WO2019048316A1 - Procédé de préparation de ferrocène, de ruthénocène et d'osmocène substitués ainsi que des matières préparées selon ce procédé - Google Patents

Procédé de préparation de ferrocène, de ruthénocène et d'osmocène substitués ainsi que des matières préparées selon ce procédé Download PDF

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WO2019048316A1
WO2019048316A1 PCT/EP2018/073279 EP2018073279W WO2019048316A1 WO 2019048316 A1 WO2019048316 A1 WO 2019048316A1 EP 2018073279 W EP2018073279 W EP 2018073279W WO 2019048316 A1 WO2019048316 A1 WO 2019048316A1
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substituted
ferrocene
osmocene
ruthenocene
mol
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Jan Klett
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Johannes Gutenberg-Universität Mainz
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System

Definitions

  • the present invention relates to a process for the preparation of substituted ferrocene, substituted ruthenocene and substituted osmocene, as well as ferrocene-containing polymers and materials produced by the process.
  • Substituted ferrocenes and ferrocene units (Fe (C 5 H (5- n) X n ) (C 5 H (5 _ m) X m ) containing 0 ⁇ n, m ⁇ 4) polymers are characterized by unique properties. This is especially true of their redox chemical, optical and catalytic properties, which enable applications in supramolecules, nano-particles, battery materials, liquid crystals, non-linear optical materials and sensors (D. Astruc, Eur. J. Inorg. Chem. 2017, 6-29).
  • the present invention effects the functionalization of ferrocene in a simple reaction. This is made possible by the four-fold metallation of commercially available ferrocene and the subsequent reaction with electrophiles.
  • multiple (> twofold) substituted ferrocenes had to be generated by prior synthesis of the underlying substituted cyclopentadiene moieties and reaction with ferrous halides (AK Diallo, J. Ruiz, D. Astruc, Inorg. Chem. 2010, 49, 1913 -1920).
  • Direct access to tetra-substituted ferrocenes has already been described by Holthausen, Wagner and coworkers (Scheibitz, M. Boite, JW Bats, H.-W. Lerner, I.
  • a common and elegant method involves the direct metalation of ferrocene, in which one or more hydrogen atoms of the cyclopentadienide rings are replaced directly by metal atoms (usually alkali metals) through organometallic bases (Scheme 1). These metals in turn can easily be replaced by suitable reagents through functional groups. As a result, ferrocene molecules can be purposefully functionalized and thereby obtain desired properties, which are required in the abovementioned applications.
  • the present invention uses an organometallic, alkane-soluble potassium base which is prepared by combining neopentyl lithium (RR Schröck, J. D. Fellmann, J. Am. Chem. Soc., 1978, 100, 3359-) to produce tetra-metallated ferrocene. 3370) and potassium alkoxide.
  • RR Schröck, J. D. Fellmann, J. Am. Chem. Soc., 1978, 100, 3359- neopentyl lithium
  • carboxylic acids of the ferrocene can be easily converted into the corresponding carboxylic acid methyl esters.
  • the reagent used is trimethylsilyldiazomethane or a solution of boron trifluoride in methanol. Since the methyl ester of l, l ', 3,3'-tetracarboxylic acid is considerably less soluble than the esters of tri- and dicarboxylic acids, the former can be easily obtained by filtration in good yield and good purity.
  • the methyl esters of tri- and dicarboxylic acids in solution can be readily purified by column chromatography.
  • the l, l ', 3,3'-substituted ferrocene according to the invention in particular l, 3,3'-metallated ferrocene, l, l', 3,3'-ferrocenetracarboxylic acid and l, l ', 3,3'-Ferrocentetracarbon Acidmethylester provide the basis for the simple synthesis of a variety of new compounds, preferably using methods known in the art.
  • ferrocene can be converted by oxidation into a double-bond polyferrocenyl (Scheme 3).
  • Scheme 3 This is, in contrast to known polyferrocenes with simple linkages, characterized by double linkages of ferrocene units to chains or networks. The strong and close linkage of the ferrocene units with each other gives such polymers new electronic properties.
  • l, r, 3,3'-metallated ferrocene can be mixed with various electrophiles, e.g. Halides are converted to corresponding l, l ', 3,3'-substituted ferro cenderivaten (Scheme 3). These include in particular the l, l ', 3,3'-halogen-substituted ferro cenderivate for the preparation of Po ly ferro cenyl and ferrocene-containing copolymers.
  • the four carboxy groups of the l, l ', 3,3'-ferrocenetracarboxylic acid can be used as ligands for the complexation of metal ions.
  • the 1,1, 3, 3 '-errocenetetracarboxylic acid plays the role of a bridging ligand and, depending on the property of the metal ion, allows the formation of complex network or lattice-like structures (metal organic frameworks, MOFs).
  • Scheme 4 schematically illustrates linkage patterns of ferrocene units in ferrocene-containing polymers.
  • the methyl ester groups according to the invention synthesized l, l ', 3,3'-Ferrocentetramethylester, such as l, l', 3,3'-Ferrocentetramethoxycarbonyl be by reaction with
  • Scheme 5 exemplifies the various possibilities for the derivatization and polymerization of ferrocene substituted according to the invention, starting from quadruple with potassium l, ', 3,3'-metallated ferrocene.
  • Ferrocene compounds are reversibly oxidizable and are used as chemical or electrochemical oxidizing and reducing agents. By removing or adding electrons, the energy levels for electron transitions and optical properties shift. Upon oxidation, the absorption lines shift towards longer wavelengths in the visible wavelength range as well as in the UV. The oxidation-related shifts can be detected spectroscopically. Accordingly, ferrocene compounds are used in chemical sensors in the visible wavelength range and in UV as redox indicators.
  • the ferrocene compounds can be electrochemically or chemically oxidized / reduced and interact as soluble or solid redox mediators with target molecules.
  • ferrocene compounds are outstandingly suitable as SET reagents (single electron transfer).
  • Measurements show a remarkably high oxidation potential of -0.75 V compared to -0.5 V for 1,1 ', 3-ferrocentrimethoxycarbonyl and -0.25 V for ferrocenedimethoxycarbonyl.
  • the present invention has for its object to provide a process for the preparation of substituted ferro cens and ferro cene-containing polymers, wherein the substituted ferro cene and the ferro cene-containing polymer an increased proportion of four-membered ferrocene or four-bonded ferrocene units contain.
  • a process for the preparation of substituted ferrocene, substituted ruthenocene, substituted osmocene and ferrocene-containing polymers comprising a step (a) in which ferrocene (bis (r- 5- cyclopentadienyl) iron), ruthenocene (bis (n 5 -cyclopentadienyl) mthenium) or osmocene (bis (n 5 -cyclopentadienyl) osmium) with an organometallic base of lithium neopentyl (LiNp, LiCH 2 C (CH 3 ) 3) and a Alkali alcoholate is reacted to l, r, 3,3'-metallated ferrocene, l, r, 3,3'-metallated ruthenocene or l, 3,3'-metallated Osmocen the structure
  • Y is iron (Fe), ruthenium (Ru) or osmium (Os) and M is an
  • Alkali metal is.
  • step (a) ferrocene (bis (r
  • potassium tert-pentoxide ie potassium tert-amylate, KOtAm or CH 3 CH 2 C (CH 3 ) 2 OK
  • a potassium alkoxide or a sodium alkoxide and n-butyllithium CH 3 (CH 2 ) 3 Li
  • the organometallic base has the structural formula IQNpiOtAmb or Na 4 Np (OtAm) 3, wherein Np is a neopentyl group having structural formula CH 2 C (CH 3 ) 3 and OtAm a tert-amyloxide group having structural formula OC (CH 3 ) 2 (CH 2 CH 3 );
  • reaction of ferrocene, ruthenocene or osmocene with the organometallic base is carried out in a reaction mixture containing an organic solvent such as n-hexane, n-heptane, n-pentane, cyclohexane, tetrahydrofuran or
  • reaction of ferrocene, ruthenocene or osmocene with the organometallic base is carried out in a reaction mixture comprising an organic solvent selected from the group comprising methanol; ethanol; Propan-l-ol; Butanediol; Pentan-l-ol; Hexane-1-ol; Heptane-l-ol; Octane-l-ol; Nonan-l-ol; Decan-l-ol; Undecan-l-ol;
  • Dodecane-l-ol Tridecane-l-ol; Tetradecane-l-ol; Pentadecane-l-ol; Hexadecane-l-ol;
  • Octadecane-l-ol Hexacosane-l-ol; 1-triacontanol; Propane-2-ol; Butane-2-ol; 2-methylpropan-1-ol; 2-methyl propane-2-ol; Pentane-2-ol; Pentane-3-ol; 2-methylbutan-l-ol;
  • Nonane-l, 9-diol Decane-l, 10-diol; Propane-l, 2,3-triol; cyclopentanol; Cyclohexanol;
  • Y is iron (Fe), ruthenium (Ru) or osmium (Os), and R is a functional group or an electrophile such as COOH, OH, Cl, Br, I, S0 2 Cl, S0 2 Br, S0 2 is I or SiMe 3 ;
  • metallated ferrocene, metalated ruthenocene or metallated osmocene from step (a) is reacted with I (iodine) to form 1, 1 ', 3,3'-substituted ferrocene, 1, ⁇ , 3,3'-substituted
  • ruthenocene or 1, l ', 3,3'-substituted osmocene of structure (II) with R I;
  • metallated ferrocene, metallated ruthenocene or metallated osmocene from step (a) is reacted with carbon dioxide (C
  • step (b) metallated ferrocene, metallated ruthenocene or metallated osmocene from step (a) with carbon dioxide (C0 2 ) and dilute hydrochloric acid is reacted
  • step (b) takes place in a protective gas atmosphere of one or more inert gases, such as argon (Ar) or nitrogen (N 2 );
  • inert gases such as argon (Ar) or nitrogen (N 2 );
  • step (b) the reaction in step (b) excluding oxygen (0 2 ) and water (H 2 0)
  • step (c) substituted ferrocene, substituted ruthenocene or substituted osmocene from step (b) is reacted with a further compound; - in step (c) substituted ferrocene, substituted ruthenocene or substituted osmocene from step (b) is esterified;
  • step (c) COOH-substituted ferrocene, COOH-substituted ruthenocene or COOH-substituted osmocene from step (b) is reacted with trimethylsilyldiazomethane (Me3SiCHN 2 ) or BF 3 / methanol to give l, l ', 3,3'- Ferrocentetramethoxycarbonyl, 1, ⁇ , 3,3'-ruthenocentetramethoxycarbonyl or l, l ', 3,3'-osmocentetramethoxycarbonyl of the structure
  • step (IV) wherein Y is iron (Fe), ruthenium (Ru) or osmium (Os) and Me is a methyl group; in step (c) COOH-substituted ferrocene, COOH-substituted ruthenocene or COOH-substituted osmocene from step (b) is reacted to form l, l ', 3,3'-substituted ferrocene, l, l', 3,3 ' -substituted ruthenocene or 1, l ', 3,3'-substituted osmocene of the structure
  • step (c) iodo-substituted ferrocene, iodine-substituted ruthenocene or iodine-substituted osmocene from step (b) is reacted with copper acetate (Cu (OOCMe) 2 )
  • OOCMe-substituted ferrocene (acetate-substituted ferrocene), OOCMe-substituted ruthenocene (acetate-substituted ruthenocene), or OOCMe-substituted osmocene (acetate-substituted osmocene);
  • step (c) iodo-substituted ferrocene, iodo-substituted ruthenocene or iodo-substituted osmocene from step (b) is reacted with copper acetate (Cu (OOCMe) 2 ) to form l, l ', 3,3'-ferrocenetraacetate, l, l ', 3,3'-ruthenocentetraacetate or l, l', 3,3'-osmocentetraacetate of the structure
  • Y is iron (Fe), ruthenium (Ru) or osmium (Os);
  • step (d) acetate-substituted ferrocene, acetate-substituted ruthenocene or acetate-substituted osmocene from step (c) is hydrolyzed to hydroxide-substituted
  • step (d) acetate-substituted ferrocene, acetate-substituted ruthenocene or acetate-substituted osmocene from step (c) is hydrolyzed to give l, l ', 3,3'-ferrocentetrahydroxide, 1, l', 3,3'- Ruthenocentetrahydroxide or l, l ', 3,3'-osmocentetrahydroxide of the structure
  • step (h) metallated ferrocene from step (a) is polymerized by oxidation to polyferrocenyl containing l, l ', 3,3'-bonded ferrocene units of structure (X);
  • metallated ferrocene from step (a) is polymerized by oxidation with an oxidizing agent selected from 1,1,2,2-tetrabromoethane, CuBr-SMe 2 and benzoyl chloride to give polyferrocenyl, which is 1, l ', 3,3'-bonded ferrocene units of structure (X);
  • step (i) substituted ferrocene from step (a), (b), (c), (d), (e), (f) or (g)
  • step (i) COOH-substituted ferrocene from step (b) or (e) is copolymerized by Kolbe electrolysis to a copolymer containing l, l ', 3,3'-bonded ferrocene units of structure (X) ;
  • step (i) iodo-substituted ferrocene from step (b) or (g) is copolymerized to a copolymer containing l, l ', 3,3'-bonded ferrocene units of structure (X);
  • step (i) iodo-substituted ferrocene from step (b) or (g) is copolymerized using a reagent selected from Cu-biphenyl and Cu (I) -thiophene-2-carboxylate to give a copolymer which has l, l ' Containing 3,3'-bonded ferrocene units of structure (X); and or
  • step (i) substituted ferrocene from step (b), (c), (d), (e), (f) or (g) is copolymerized by ring-opening the polymerization to give a copolymer containing 1, ⁇ , 3,3 '- bound ferrocene units of structure (X) contains.
  • the object of the invention is to provide substituted ferrocene, substituted ruthenocene or substituted osmocens, as well as ferrocene-containing polymers which contain an increased proportion of tetra-substituted ferrocene, tetra-substituted ruthenocene or quadruply-substituted osmocene or quadruple-bonded ferrocene units.
  • the invention relates to substituted ferrocene, substituted ruthenocene and substituted osmocene which can be prepared by a process comprising step (a) or step (a) and one or more of steps (b), (c), (d), ( e), (f) and (g).
  • the invention relates - Substituted ferrocene, the> 50 mol% of l, l ', 3,3'-substituted ferrocene, based on the totality of the ferrocene units, contains;
  • the substituted ferrocene contains> 60 mol%
  • the substituted ruthenocene contains> 60 mol%
  • Ruthenocene based on the totality of the ruthenocene units.
  • the substituted osmocene contains> 60 mol%
  • the invention relates
  • Y is iron (Fe), ruthenium (Ru) or osmium (Os) and M is an alkali metal such as potassium, sodium or lithium
  • R is a functional group or an electrophile such as COOH, OH, Cl, Br, I, S0 2 C1, S0 2 Br, S0 2 I or SiMe 3 and X is one
  • Substituent selected from the group comprising CH 2 OH, COC1, CON 3 , NCO, NHCOOMe, NHBoc, NH 2 , CHO (formyl), CH CH 2 (vinyl).
  • the substituted ferrocene contains l, l ', 3,3'-substituted ferrocene of the structure
  • M is an alkali metal such as potassium, sodium or lithium
  • R is a functional group or an electrophile such as COOH, OH, Cl, Br, I, S0 2 Cl, S0 2 Br, S0 2 I or SiMe3
  • the substituent R of the l, l ', 3,3'-substituted ferrocene of structure (II) is not SiMe 3 (trimethylsilyl).
  • the substituted ruthenocene contains 1, ⁇ , 3,3'-substituted ruthenocene of the structure
  • M is an alkali metal, such as potassium, sodium or lithium
  • R is a functional group or an electrophile, such as COOH, OH, Cl, Br, I, S0 2 C1
  • the substituted osmocene contains l, l ', 3,3'-substituted osmocene of the structure
  • M is an alkali metal such as potassium, sodium or lithium
  • R is a functional group or an electrophile such as COOH, OH, Cl, Br, I, S0 2 Cl, S0 2 Br, S0 2 I or SiMe3
  • the invention relates to Po ly ferro cenyl, which can be prepared by polymerization of metallated ferrocene from step (b) and l, l ', 3,3'-bound ferrocene units (Fe (C 5 H 3 ) 2 ) of the structure contains.
  • the invention furthermore relates to poly ferrocenyl which contains> 20 mol% of 1, 1 ', 3,3'-bonded ferrocene units (X), based on the totality of all the monomers of the polyferenocenyl.
  • the poly ferro cenyl contains> 30 mol%,> 40 mol%,> 50 mol%,> 60 mol%,> 70 mol%,> 80 mol%,> 90 mol% % or> 95 mol% of l, l ', 3,3'-bonded ferrocene units (X), based on the totality of all monomers of the polyferrocenyl.
  • the invention relates to ferrocene-containing copolymer which can be prepared by copolymerization of substituted ferrocene from one of the steps (b), (c), (d), (e), (f) or (g) and l, l ''3,3'-bonded ferrocene units (Fe (C5H 3 ) 2 ) of the structure
  • the invention relates to ferrocene-containing copolymer containing> 1 mol% of 1, ⁇ , 3,3'-bound ferrocene units of the structure (X), based on the totality of all monomers of the ferro cene-containing copolymer.
  • the ferro cene-containing copolymer contains> 5 mol%,> 10 mol%,> 20 mol%,> 30 mol%,> 40 mol% or> 50 mol% of 1, unbound Ferrocene units of structure (X), based on the totality of all monomers of the ferro cene-containing copolymer. In an advantageous embodiment, the ferro cene-containing copolymer contains> 20 mol%,
  • substituted ferrocene refers to a mixture of unreacted ferrocene and various 1- or multi-substituted ferrocene compounds, a mixture of unreacted ruthenocene and various 1- or multiply substituted ruthenocene compounds and respectively a mixture of unreacted osmocene and various mono- or polysubstituted osmocene compounds.
  • Substituted ferrocene in the sense of the invention includes, inter alia, ferrocene compounds, ruthenocene compounds or respective osmocene compounds having the following structures and their isomers
  • Y is iron (Fe), ruthenium (Ru) or osmium (Os), the mixture> 5 mol%,> 10 mol%,> 20 mol%,> 30 mol%,> 40 mol% and in particular> 50 mol% of l, r, 3,3'-substituted ferrocene of structure (IIa), l, l ', 3,3'-substituted ruthenocene of structure (IIa) or respectively 1, l', 3 , 3'-substituted osmocene of structure (IIa) and Z is an alkali metal, such as potassium or sodium, a functional group or an electrophile, such as COOH, COOMe, Cl, Br, I, S0 2 C1, S0 2 Br, S0 is 2 I or SiMe 3 or a substituent selected from the group comprising CH 2 OH, COCl, CON 3 , NCO, NHCOOMe, NHBoc,
  • step (a) Alkali alcoholate is reacted.
  • substituted ferrocene substituted ruthenocene
  • substituted osmocene within the meaning of the invention can be prepared according to step (a) in conjunction with one or more of steps (b), (c), (d), (e) , (f), (g).
  • FIG. 1 shows the crystal structure of the organometallic base K 4 Np (OtAm) 3 , which is formed by reacting lithium neopentyl (LiNp, LiCH 2 C (CH 3 ) 3 ) with potassium alkoxide;
  • Fig. 2 shows the molecular configuration of crystalline 1, 1 ', 3,3'-ferrocenetramethoxycarbonyl
  • Fig. 3 shows the NMR spectrum of 1, l ', 3,3'-ferrocenetetracarboxylic acid
  • Fig. 4 shows the NMR spectrum of a mixture of ferrocenedicarboxylic acid, tricarboxylic acid and tetracarboxylic acid;
  • Fig. 5 is the NMR spectrum of 1, l ', 3,3'-ferrocenetramethoxycarbonyl;
  • Fig. 6 shows the NMR spectrum of 1,1 ', 3-Ferrocentrimethoxycarbonyl.
  • Example 1 Neopentyllithium (LiNp.LiCH.tBu)
  • Neopentyllithium (LiNp, LiCH 2 tBu) can be obtained in yields of 60-80% yields on a gram scale (RR Schröck, JD Fellmann, J. Am. Chem. Soc., 1978, 100, 3359-3370).
  • Potassium tert-pentoxide ie, potassium tert-amylate, KOtAm, and CH 3 CH 2 C (CH 3 ) 2 OK, respectively
  • a suitable solution in cyclohexane is available from TCI Europe (1 mol / l).
  • Sigma-Aldrich solutions are available in toluene or THF. The solvent used is exclusively hexane, which has been dried over potassium and distilled under an argon protective gas atmosphere. All steps of the syntheses were carried out under an argon blanket gas atmosphere.
  • K (otam) 3 KNP "3KOtAm
  • LiNp 0.078 g, 1.0 mmol, 1.0 eq
  • KOtAm 0.560 g, 4.5 mmol, 4.5 eq
  • the yellowish solution was stored for several days at -30 ° C, the compound K 4 Np (OtAm) 3 was obtained as colorless, very air-sensitive crystals. Yield 0.30 g (0.61 mmol, 61%).
  • the organometallic base K 4 Np (OtAm) 3 crystallizes in a structure (see FIG. 1) with the following parameters: Monoclinic, P 2 c
  • Example 3 Tetrapotassium-l. ferrocene-.3.3'. FefCj LK? ?
  • Example 5 l. .3.3'-Ferrocentetracarbon Acid. FefCj LfCOOH? ? using? -butyllithium Unlike Example 4, KOtAm (0.560 g, 4.5 mmol, 4.5 eq) was weighed out and stored
  • Example 6 l. .3.3'-Ferrocentetramethoxycarbonyl. FefCj LfCOOMe? ?
  • Example 7 I'rjJ'-ferrocenetrachlorocarbonyl. FeiiC ⁇ YCOCl ⁇
  • Fe [(C 5 H 3 ) (COOH) 2 ] 2 (79.67 g, 0.22 mol) was suspended in 225 mL CHCl 3 and pyridine (0.5 mL, 3 mol%) and oxalyl chloride (120 mL, 6.4 equiv).
  • the reaction mixture was heated to reflux and stirred at the reflux temperature for 3 h.
  • the bulk of gas, including HCl was formed and neutralized with 10% NaOH solution.
  • the solvent and excess oxalyl chloride were removed under vacuum to give Fe [(C 5 H 3 ) (COCl) 2] 2 as a dark red solid intermediate.
  • the intermediate was dissolved in 675 mL acetone and NaN 3 (63.2 g, 4.4 equiv) dissolved in 90 mL water was added with vigorous stirring.
  • the intermediate was dissolved in 675 mL acetone and NaN 3 (63.2 g, 4.4 equiv) dissolved in 90 mL water was added with
  • reaction mixture was stirred at 50 ° C for 1.5 h, whereupon NaCl formed. Subsequently were added 100 mL of saturated NaHC0 3 and the reaction mixture to two 2 L
  • Reaction mixture in both beakers was cooled by ice to precipitate the product completely. Using a coarse glass frit filter, the reaction mixture was filtered and the product was washed with 3-4 L of water. The resulting red solid was air dried, vacuum dried, lightly ground and sieved.
  • the crystallized product was isolated by further filtration, washed with a 2: 1 mixture of hexane and toluene and dried under vacuum to give a yellow crystalline solid. From the mother liquor additional product can be extracted. The product is reasonably stable but should be protected from moisture. Yield: 81% (57.1 g) of yellow-brownish, microcrystalline solid.
  • the eluate was concentrated to a small volume of ethyl acetate to crystallize the product.
  • Ferro cen-tetracarboxylic acid was converted by reduction using lithium aluminum hydride (L1AIH 4 ) in three and four times CFLOH-substituted ferrocenes (ferrocene-trihydroxymethyl and ferrocene-tetrahydroxymethyl).
  • L1AIH 4 lithium aluminum hydride
  • ferrocene is replaceable by ruthenocene or osmocene. Also, the respective substituted derivatives of ferrocene, ruthenocene and osmocene behave chemically in an analogous manner.
  • RuCi 0 H 6 (COOMe) 4 (0.052 g, 58%) as a light yellow crystalline powder.
  • RuCioH 6 (COOMe) 4 :
  • IR (CsBr plates, Nujol muH): 1730, 1462, 1357, 1316, 1263, 1201, 1165, 1076, 959, 909, 861, 837, 773, 731, 575, 518, 472 cm -1 .
  • Osmocene (0.062 g, 0.19 mmol) was added and stirred for 1 h at 60 ° C. This was immediately followed by a precipitation with white-gray color. After cooling, dried carbon dioxide was added to the solution using P4O10 until the color changed to a pale yellow. After addition of HCl (10%, 20 mL) the solution was filtered and the filter retentate was washed with water and dried under vacuum to give as product a pale yellow solid (0.061 g).
  • OsCi 0 H 6 (COOMe) 4 (0.025 g, 24%) as pale yellow crystalline powder.
  • IR (CsBr plates, Nujol mull): 1736, 1462, 1352, 1311, 1263, 1201, 1164, 1076, 1048, 958, 908, 843, 769, 731, 603, 572, 510, 465 cm -1 .
  • IR (CsBr plates, Nujol muH): 1732, 1718, 1603, 1463, 1347, 1306, 1276, 1199, 1159, 1074, 1027, 959, 906, 841, 769, 732, 669, 600, 570, 514, 459cm "1 .
  • Substituted ferrocene referred to mixtures of unreacted ferrocene and various 1 to 4 times substituted ferrocene compounds having a high proportion of 1, ⁇ , 3,3'-substituted ferrocene of the structure (IIa).
  • the molar fraction of l, l ', 3,3'-substituted ferrocene of structure (IIa) is determined by means of quantitative nuclear magnetic resonance spectroscopy - referred to below as qNMR.
  • qNMR has been established for about 15 years in chemical and in particular pharmaceutical research (Importance of Purity Evaluation and the Potential of Quantitative ! HNMR as a Purity Assay; GF Pauli, S.N. Chen, C. Simmler, DC Lankin, T.). Gödecke, BU Jaki, JB Friesen, JB McAlpine, JG Napolitano, J. Med.
  • exemplary 1H NMR spectra of some 2- to 4-fold substituted in Table 1 with numeral (i) to (v) designated Ferro centagen reproduced.
  • the associated 1H NMR resonance peaks are marked in FIGS. 3 to 6 and Table 1 with the letters a to k and a ', b', c 'and d'.
  • Table 1 shows the position or shift of the respective NMR resonance peak and its intensity or peak area.
  • the peak area is determined using device-specific or generic software packages such as INFOS (INFOS: spectrum fitting software for NMR analysis, AA Smith, J. Biomol., NMR, February 2017, Volume 67, Issue 2, pp 77-94) by nonlinear regression or Fourier analysis certainly.
  • INFOS information: spectrum fitting software for NMR analysis, AA Smith, J. Biomol., NMR, February 2017, Volume 67, Issue 2, pp 77-94
  • m1 H contribution 1 proton contribution, hereinafter also referred to as m1 H contribution ", wherein preference is given to undisturbed 1 H resonance peaks of the respective ferrocene compound which are not superimposed with other 1 H resonance peaks calculated by
  • n is an integer> 1;
  • the ferrocene compounds of the type (i) (1, 1 ', 3,3'-ferrocenetracarboxylic acid) include the 1H NMR resonance peaks denoted by a and b, b having the 1H NMR resonance peak d of the
  • the ferrocene compound of the type (ii) (l, l ', 3,3'-ferrocene-tricarboxylic acid) the
  • Table 2 ⁇ contributions according to the NMR spectrum of FIG. 4 The ratios of the H contributions of each of the two ferrocene compounds (i), (ii) and (iii) are consistent; it applies
  • the molar fractions reported in Table 3 were verified by independent 1H qNMR measurements on three calibrated mixtures.
  • the calibrated mixtures were prepared from agglomerated ferrocene compounds of type (i), (ii) and (iii).

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Abstract

Procédé de préparation de ferrocène substitué, de ruthénocène substitué et d'osmocène substitué ainsi que de polymères contenant du ferrocène, lesquels possèdent des motifs ferrocènes substitués en 1,1', 3,3', des motifs ruthénocènes substitués en 1,1', 3,3' et des motifs osmocènes substitués en 1,1', 3,3' respectifs ainsi que des matières préparées selon ledit procédé.
PCT/EP2018/073279 2017-09-07 2018-08-29 Procédé de préparation de ferrocène, de ruthénocène et d'osmocène substitués ainsi que des matières préparées selon ce procédé WO2019048316A1 (fr)

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DE102017008407.6A DE102017008407A1 (de) 2017-09-07 2017-09-07 Verfahren zur Herstellung von substituiertem Ferrocen und Ferrocen-haltigen Polymeren sowie nach dem Verfahren hergestellte Stoffe
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4137498A1 (fr) * 2021-07-30 2023-02-22 Palo Alto Research Center Incorporated Composés à activité redox et leurs utilisations

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